The present invention relates to a novel class of degradable, amorphous fluorochemical acrylate monomers, oligomers, and/or polymers containing pendant branched fluoroalkyl groups that may exhibit low surface energy and improved environmental compatibility.
In the art of repellent treatments for substrates, fluorochemicals have found extensive use for nearly half a century as low surface energy materials for imparting repellency to a variety of substrates. For an overview of fluorochemical repellents, see Mason Hayek, Waterproofing and Water/Oil Repellency, 24 Kirk-Othmer Encyclopedia Of Chemical Technology 448-455, 460-462, 3rd ed. (1979).
The treatment of fibrous substrates (e.g., carpets, fabrics, leather, nonwovens and paper) with fluorochemicals to render them repellent to water and oil-based stains and resistant to dry soil has been well documented in the art. Successfully treated with these fluorochemical repellents, such fibrous substrates resist the discoloration that results from normal staining and soiling and thus retain their original aesthetic appeal. A wide variety of such fluorochemical repellents are known and described in the art. Among them are the fluorochemical acrylate polymers disclosed in U.S. Pat. No. 3,341,497 (Sherman et al.) and U.S. Pat. No. 3,462,296 (Raynolds et al.), fluorochemical carbodiimides disclosed in U.S. Pat. No. 3,896,251 (Landucci), fluorochemical esters disclosed in U.S. Pat. No. 3,923,715 (Dettre), U.S. Pat. No. 4,029,585 (Dettre), and U.S. Pat. No. 4,264,484 (Patel) and fluorochemical urethanes and ureas disclosed in U.S. Pat. No. 3,398,182 (Guenthner et al.), U.S. Pat. No. 4,001,305 (Dear et al.), U.S. Pat. No. 4,792,354 (Matsuo et al.) and U.S. Pat. No. 5,410,073 (Kirchner). Commercial fluorochemical repellents of these various types are widely available and are sold, for example, under the SCOTCHGARD and TEFLON trademarks.
Also important is the treatment of hard surface substrates, such as masonry, stone and glass, with repellents to retard the discoloration of the masonry or stone from exposure to water- and oil-based stains and deterioration from spalling and efflorescence. Fluorochemical repellents for masonry and stone are known. U.S. Pat. No. 5,274,159 (Pellerite et al.) describes certain water-soluble or dispersible fluorocarbylalkoxysilane surfactants that may be cured onto a masonry surface. U.S. Pat. No. 6,037,429 (Linert et al.) discloses water-soluble treatments for masonry and stone containing fluorochemical polymers having pendent fluoroaliphatic, carboxyl, (poly)oxyalkylene and optional silyl groups.
In addition to being useful as repellents, fluorochemical polymers have found use as low refractive index coatings for glass optical fibers to help retain the light in the fiber. U.S. Pat No. 5,223,593 (McAllister et al.) describes optical fiber coatings made from homopolymers of 1,1-dihydroperfluorocyclohexylmethyl methacrylate.
Particularly useful as repellents are fluorochemicals containing long chain perfluoroalkyl moieties (i.e., C6F13xe2x80x94 to C12F25xe2x80x94), as such moieties impart very low surface energy to the substrate surface and thus provide the treated substrate with excellent water and oil repellency. (See, for example, H. C. Fielding, xe2x80x9cOrganofluorine Compounds and Their Applications,xe2x80x9d R. E. Banks, Ed., Society of Chemical Industry, p. 214 (1979).) Especially preferred from both cost and performance standpoints are fluorochemical repellents containing primarily straight-chain perfluorooctyl (C8F17xe2x80x94) moieties. It is thought, but not relied upon that such repellents (those containing perfluorooctyl moieties) impart a high degree of repellency to a treated substrate because the perfluoroalkyl groups align to form an ordered, low energy, liquid crystalline-like structure at the substrate surface. This liquid crystalline-like structure, is normally formed by heating the substrate treated with a polymer containing perfluorooctyl moieties, to an elevated temperature, e.g., from about 100xc2x0 C. to about 150xc2x0 C., to properly orient the perfluoroalkyl chains.
However, perfluorooctyl group-containing polymers can ultimately degrade to form functional perfluorooctyl-containing compounds. It has been reported that certain functional perfluorooctyl-containing compounds may tend to bio-accumulate in living organisms. This tendency has been cited as a potential concern with regard to some fluorochemical compounds. For example, see U.S. Pat. No. 5,688,884 (Baker et al.).
As a result, there is a desire for new fluorine-containing compounds that can effectively provide water- and oil-repellent properties and can be eliminated more effectively from the body (both the polymer/oligomer and its degradation products). One approach has been to replace the C6F13xe2x80x94 to C12F25xe2x80x94 perfluoroalkyl moieties in the compound with shorter chain analogues (i.e., C3-C5 moieties). For example, U.S. patent application Ser. No. 09/803702 describes water- and oil-repellent urethane oligomers containing at least one pendant C4F9xe2x80x94 repeatable unit and at least one C4F9xe2x80x94 terminal group. Published World Patent Application WO 01/30873 describes fluorochemical sulfonamide polymeric surfactants having at least one pendant group containing a C4F9xe2x80x94 or C3F7xe2x80x94 moiety.
The acrylate monomer CF3CF2CF2OCF(CF3)CH(CF(CF3)2)(OC(O)CHxe2x95x90CH2) is known. Also known is the acrylate monomer CF2CF2CF3CH(CF3)C(O)CHxe2x95x90CH2 and its polymers and copolymers. The diacrylate monomer CH2xe2x95x90CHC(O)OCH(CF(CF3)2)xe2x80x94(CF2)8xe2x80x94CH(CF(CF3)2)(OC(O)CHxe2x95x90CH2) and its preparation are disclosed in Published World Application WO 00/50517, as well as the conversion of the diacrylate monomer to a polymer by UV curing with a photoinitiator.
In one aspect, this invention relates to compounds comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2), wherein Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
In another aspect, this invention relates to a method of treating a substrate to render it oil-and/or water-repellent comprising treating the substrate with a composition comprising a compound that comprises at least one acrylate monomer, said monomer comprising at least one pendant group of the structure xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2), wherein Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
In still another aspect, this invention relates to a method of reducing the surface tension of a liquid comprising adding to the liquid a compound comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2), wherein Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
In yet another aspect, this invention relates to an article comprising a substrate treated with a composition comprising a compound comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2), wherein Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
In addition to exhibiting surface energies comparable to known fluorochemical compounds containing pendant straight-chain perfluorooctyl (C8F17xe2x80x94) or perfluorobutyl (C4F9xe2x80x94) groups, the compounds of this invention containing pendant xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2) groups offer two additional advantages. First, the compounds of this invention generally resist hydrolysis under application conditions, possibly due to steric effects caused by the branched fluoroalkyl chain (e.g., in contrast to polymers made by polymerizing RfCH2OC(O)CHxe2x95x90CH2, where Rf is a straight chain or branched perfluoroalkyl group). Second, the expected ultimate degradation products of compounds of this invention will generally have minimal adverse environmental effects because these degradation products have a low molecular weight. Oxidation and/or hydrolysis of the compounds will release the fluorinated alcohol or ketone. These ketones have at least 5 carbon atoms and have recently been shown to exhibit low toxicity, in contrast to lower carbon atom-containing perfluoroketones such as CF3C(O)CF3, which can be very toxic. Furthermore, some perfluorinated ketones of the formula RfC(O)Rfxe2x80x2 and their corresponding alcohols are known to be cleaved by strong bases to form RfCOOH plus Rfxe2x80x2H, suggesting that their environmental lifetimes will be short compared with linear Rf protective groups. This ketone degradation is especially facile when Rfxe2x80x2 is (CF3)2CFxe2x80x94.
Also, due perhaps to the lack of crystallinity of the amorphous branched perfluoroalkyl groups and absence of a clearly defined melt transition temperature, the compounds of this invention do not require curing at elevated temperatures in order to develop their repellent properties and thus can be cured at ambient conditions. In contrast, known polymers containing the core crystalline pendant straight-chain perfluoroalkyl groups (e.g., C8F17xe2x80x94 or C4F9xe2x80x94) require heat treatment to orient the perfluoroalkyl groups properly in order to fully develop their repellent properties.
This invention relates to novel amorphous, degradable fluorochemical compounds comprising at least one acrylate monomer comprising polymerizable or a polymer chain of units of the monomer, said compound having at least one pendant group of the structure xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2), wherein Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
The compounds of this invention which are also referred to herein as monomers, oligomers, or polymers of this invention, and fluorochemical acrylate monomers, oligomers, or polymers of the invention can generally be depicted as shown in Formula I: 
wherein  represents a bond in a polymerizable or a polymer chain;
Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms;
Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms;
R is hydrogen, methyl, fluoro or chloro; and
x is at least 1.
Preferred monomer compounds are depicted in Formula II:
CH2xe2x95x90C(R)xe2x80x94C(O)xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2)xe2x80x83xe2x80x83(II)
wherein
R is hydrogen, methyl, fluoro or chloro; and
Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms; and
Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms.
Fluorochemical acrylate polymers of this invention contain within the polymer backbone (co)polymerized units having the formula depicted in Formula III: 
wherein
R is hydrogen, methyl, fluoro or chloro; and
Rf is a straight chain or branched perfluoroalkyl group with five or less carbon atoms;
Rfxe2x80x2 is a branched perfluoroalkyl group with three to five carbon atoms; and
x is at least 2.
For Formula III, when x has a value from 2 to 10, the fluorochemical acrylate polymer can be considered an oligomer (i.e., a very low molecular weight polymer). Such oligomers are useful as surfactants for coating compositions containing high surface energy organic materials.
For Formula III, when x has a value of greater than 10 and up to about 50, the fluorochemical acrylate polymer is useful as a repellent treatment for fibrous or hard surface substrates and is useful as an optical fiber coating.
For both the acrylate monomers and polymers of this invention, Rf is preferably CF3xe2x80x94, CF3CF2xe2x80x94, CF3CF2CF2xe2x80x94, (CF3)2CFxe2x80x94 or (CF3)2CFCF2xe2x80x94 and Rfxe2x80x2 is either xe2x80x94CF(CF3)2 or xe2x80x94CF2CF(CF3)2. More preferably, Rf is CF3CF2xe2x80x94 or CF3CF2CF2xe2x80x94 and Rfxe2x80x2 is xe2x80x94CF(CF3)2.
Examples of useful xe2x80x94Oxe2x80x94CH(Rf)(Rfxe2x80x2) groups include but are not limited to xe2x80x94Oxe2x80x94CH(CF3)(CF(CF3)2), xe2x80x94Oxe2x80x94CH(CF2CF3)(CF(CF3)2), xe2x80x94Oxe2x80x94CH(CF2CF2CF3)(CF(3)2), xe2x80x94Oxe2x80x94CH(CF(CF3)2)2 and xe2x80x94Oxe2x80x94CH(CF2CF(CF3)2)2.
The novel fluorochemical acrylate monomers of this invention can be prepared for example by reacting an alcohol of the formula HOxe2x80x94CH(Rf)(Rfxe2x80x2) with an acryloyl compound of the formula CH2xe2x95x90C(R)xe2x80x94C(O)xe2x80x94X in the presence of a tertiary amine acid scavenger, wherein Rf, Rfxe2x80x2 and R are as defined for Formula II and X is a good leaving group, such as a halogen atom (e.g., Cl or F) or a hydroxyl group. The alcohol can be prepared for example by reduction with sodium borohydride of the corresponding perfluoroketone of the formula Rfxe2x80x94C(O)xe2x80x94Rfxe2x80x2; see Fokin, A. V., et al.; Bull. Acad. Sci. USSR; EN; 27; 8; 1692-1695 (1978); and Saloutina, L. V. et al; J. Org. Chem. USSR; EN; 18; 685-689 (1982).
The novel fluorochemical acrylate polymers of this invention can be made for example by homopolymerizing or copolymerizing the monomer of Formula II, employing free-radical polymerization techniques well known to one skilled in the art. Useful free-radical initiators include but are not limited to: a persulfate; an azo compound such as azoisobutyronitrile or azo-2-cyanovaleric acid; a hydroperoxide such as cumene, t-butyl, or t-amyl hydroperoxide; a dialkyl peroxide such as di-t-butyl and dicumyl peroxide; a peroxyester such as t-butyl perbenzoate or di-t-butylperoxy phthalate; a diacylperoxide such as benzoyl peroxide; lauroyl peroxide; and the like. The initiating radical formed by the initiator can be incorporated into the fluorochemical acrylate polymer to varying degrees depending on the type and amount of initiator used. A suitable amount of initiator depends on the particular initiator and other reactants being used. About 0.1 percent to about 5 percent by weight of an initiator can be used, based on the total weight of the monomers in the reaction, depending upon the desired molecular weight of the fluorochemical acrylate polymer to be made.
To further control the molecular weight of the polymer, a mono-, di-, or polythiol chain transfer agent can be employed, such as for example ethanethiol, propanethiol, butanethiol, hexanethiol, n-octylthiol, t-dodecylthiol, 2-mercaptoethyl ether, 2-mercaptoimidazole, 2-mercaptoethylsulfide, 2-mercaptoimidazole, 8-mercaptomenthone, 2,5-dimercapto-1,3,4-thiadiazole, 3,4-toluenedithiol, o-, m-, and p-thiocresol, ethylcyclohexanedithiol, p-menthane-2,9-dithiol, 1,2-ethanedithiol, 3-mercapto-1,2-propanediol, 2-mercaptopyrimidine, and the like. The chain transfer agent is generally used in an amount of about 0.025 to about 0.2 equivalents, per equivalent of combined olefinic monomers. When oligomers are desired (i.e., where x in formula I is from 2 to 10) higher levels of chain transfer agent can be employed. The repellent fluorochemical acrylate polymers of this invention are amorphous materials typically having glass transition temperatures ranging from about 0xc2x0 C. to about 60xc2x0 C.
In order to achieve the maximum repellent and refractive index properties, it is preferred that the fluorochemical acrylate polymer is a homopolymer of the fluorochemical acrylate monomer of this invention or alternatively is a copolymer of a fluorochemical acrylate monomer of the invention and another fluorine-containing acrylate monomer outside this invention such as for example CH2xe2x95x90CHC(O)OCH(CF3)2, or CH2xe2x95x90CHC(O)OCH2CF3. However, small amounts (i.e., up to about 25% by weight) of a fluorine-free comonomer, preferably a comonomer that is non-gaseous under ambient conditions, can be (co)polymerized without significantly degrading the polymer repellency properties. For surfactant applications, higher amounts of fluorine-free comonomer (i.e., up to about 80% by weight) can be (co)polymerized. Useful fluorine-free comonomers include alkyl acrylate esters, vinyl acetate, vinylidene chloride, styrene, alkyl vinyl ethers, alkyl methacrylate esters, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and N-vinylpyrrolidone. Alkyl acrylate esters are preferred fluorine-free comonomers and include straight-chain, cyclic, and branched-chain isomers of alkyl esters containing C1-C50 alkyl groups. Useful specific examples of alkyl acrylate esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, 2-butyl acrylate, iso-amyl acrylate, n-hexyl acrylate, heptyl acrylate, n-octyl acrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, and tetradecyl acrylate.
Preferably, the free-radical polymerization is carried out in solvent at any suitable concentration, e.g., from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture. Examples of suitable solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethylether, glyme, diglyme, diisopropyl ether), esters (e.g., ethyl acetate, butyl acetate), alcohols (e.g., ethanol, isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide), halogenated solvents (e.g., methylchloroform, FREON(trademark)113, trichloroethylene, xcex1,xcex1,xcex1-trifluorotoluene, fluorinated ethers such as C4F9OCH3, hydrofluorocarbons such as CF3CFHCFHCF2CF3, and the like), and mixtures thereof Preferably, the solvent is a low water-solubility solvent such as an ester (e.g., ethyl acetate or butyl acetate), a ketone (e.g., methyl ethyl ketone or methyl isobutyl ketone), or an ether (e.g., diisopropyl ketone).
The polymerization to form the desired polymer can be carried out at any temperature suitable for conducting an organic free-radical reaction. Particular temperature and solvents for use can be easily selected by those skilled in the art based on considerations such as the solubility of reagents, the temperature required for the use of a particular initiator, and the like. While it is not practical to enumerate a particular temperature suitable for all initiators and all solvents, generally suitable polymerization temperatures are between about 30xc2x0 C. and about 200xc2x0 C.
For oil- and/or water-repellent applications, compounds of the invention can be most conveniently used as an aqueous composition, in particular an aqueous dispersion in water. If the compound is first made by solution polymerization in a solvent, the polymer or oligomer can subsequently be dispersed in water by vigorously mixing the solution polymer or oligomer with water containing cationic, anionic, amphoteric and/or nonionic surfactants and, if appropriate, other auxiliaries and solvents, employing ultrasonic treatment or treatment in a high pressure homogenizer to provide the energy to form a stable dispersion. A solvent-free dispersion of the compound can then be obtained by subsequent removal via distillation of the polymerization solvent. Generally, the aqueous dispersion as a concentrate contains 5 to 50% by weight of polymer or oligomer, 0.5 to 15% by weight of one or more dispersing and/or emulsifying agents, and 0 to 30% by weight of a solvent or solvent mixture, the remainder being water. Alternatively, the aqueous fluorochemical acrylate polymer or oligomer dispersion may be produced by emulsion polymerization of the fluorochemical acrylate monomer in water in the presence of a cationic, anionic, amphoteric and/or nonionic surfactant, using a water-soluble free-radical initiator such as ammonium persulfate to initiate the polymerization.
Aqueous solutions or dispersions of the fluorochemical acrylate polymers may be topically applied onto any substrate, including fibrous substrates and hard surface substrates to render that substrate resistant to soiling and repellent to water- and oil-based stains. Any topical method of application that produces a uniform thin coating of the polymer on the substrate surface may be employed, such as immersion, flooding, spraying, padding or painting. Once applied from solution or dispersion, the polymer treatment may be dried onto the substrate either under ambient conditions or at elevated temperatures to produce a long-lasting altered surface that does not change the appearance of the substrate. In the case of porous substrates, the penetration of the polymer treatment into the porous substrate surface generally prevents significant adsorption of staining fluids into the substrate (i.e., the fluids will not soak in), even after extensive outdoor exposure, since the coating below the surface is not degraded.
Useful fibrous substrates, which may be protected when topically treated with polymers of this invention, include natural textiles and fabrics such as cotton or wool and synthetic fabrics or textiles such as polyester or nylon, as well as paper and leather(e.g., textiles, carpets, leather, nonwovens, paper). Topical treatment application to fibrous substrates can be accomplished via immersion, spray, foam, kiss roll and metering. For example, the substrate can be immersed in a dispersion or solution of the fluorochemical acrylate polymer and agitated until it is saturated. The saturated fibrous substrate can then be run through a padder/roller to remove excess dispersion, dried in an oven at a relatively low temperature (e.g., at 70xc2x0 C.) for a time sufficient to remove the dispersion medium (e.g. solvents such as those used in the polymerization reaction), and cured at a temperature and for a time sufficient to provide a cured treated substrate. This curing process can be carried out at temperatures between ambient temperature and about 150xc2x0 C. depending on the particular composition used. In general, a temperature of about 40 to 150xc2x0 C. for a period of about 10 minutes is suitable. The cured treated fibrous substrate can be cooled to room temperature and used as desired, e.g., incorporated or fashioned into apparel or upholstery.
Hard surface substrates which may be protected when topically treated with the fluorochemical acrylate polymers of this invention include porous hard surfaces such as masonry (i.e., human-made hard porous materials such as concrete, brick, tile, grout) and stone (i.e., naturally occurring porous materials), substrates used extensively in the construction of buildings, roads, parking ramps, driveways, garage flooring, fireplaces, fireplace hearths, and counter tops. When left unprotected, masonry and stone surfaces quickly discolor from exposure to water- and oil-based stains and gradually deteriorate from spalling and efflorescence induced by water penetration and weather exposure. Protection against discoloration from common water- and oil-based household liquids such as motor oil, brake-oil, transmission fluid, cooking oil, coffee, and wine is highly desirable due to the high cost and labor of replacing such materials. For these massive and immobile substrates, application of treating liquids is most conveniently done by brush, roller or spray and cure must be accomplished at ambient temperature.
The fluorochemical acrylate polymers of this invention may also be used as low refractive index coatings, particularly for coating optical fibers. Typically, optical fibers comprise a light carrying core, for example an inorganic glass such as fused silica or a polymer such as polymethyl methacrylate, and a cladding material having a lower refractive index than the core. By having a lower refractive index, the cladding material serves to confine the light energy within the core and thereby allows propagation of light by a phenomenon generally known as xe2x80x9ctotal internal reflection.xe2x80x9d Fiber-guided modulated light beams are useful in many applications, for example, telecommunications, computer link-ups, and automotive controls. Advantageously, fiber optic linkages have a greater information carrying capacity as compared to metal wires carrying electrical signals. Furthermore, fiber optics are less likely to suffer from external interference, such as electromagnetic radiation.
The fluorochemical acrylate polymers of this invention can also be employed to apply a coating to an electrical device. Such coating applications include anti-stiction coatings for computer hard drives, barrier coatings to protect sensitive substrates such as circuit boards, and antimigration coatings to prevent the migration of lubricants. Copolymers of the fluorochemical acrylate monomer with for example a small amount of (meth)acrylic acid (i.e., less than 10% by weight, preferably less than 5% by weight) can improve the adhesion of the fluorochemical acrylate polymer to polar substrates such as the metal circuits etched on circuit boards or the metallic surfaces of computer hard drives or optical pellicle frames.
The amount of the fluorochemical compound applied to a substrate in accordance with this invention is chosen so that desirably high surface modification (e.g., water and/or oil repellency, refractive index reduction) is imparted to the substrate surface, said amount usually being such that 0.01% to 5% by weight, preferably 0.05 to 2% by weight, of fluorine is present on the treated substrate. The amount, which is sufficient to impart desired repellency or refractive index reduction, can be determined empirically and can be increased as necessary or desired.
The fluorochemical acrylate polymers of this invention are also useful as surfactants for lowering the surface tension of liquids and thus can be employed to improve the wetting properties of coating compositions containing high surface energy organic materials. Such xe2x80x9cdifficult-to-wet-withxe2x80x9d materials include thermoset resins (e.g., high solids formulations containing epoxy resins, acrylic resins, aminoplasts and/or polyols) and thermoplastic resins (e.g., plasticized polyvinyl chloride dispersions). Particularly useful as surfactants are copolymers of the fluorochemical acrylate monomers of this invention with polyoxyalkylene acrylate esters, such as the acrylate esters of PLURONIC(trademark) propylene oxide/ethylene oxide copolymers (copolymers available from BASF Corp., Mount Olive, N.J.) or the acrylate esters of CARBOWAX(trademark) polyethylene glycols (glycols available from Union Carbide Corp., South Charleston, W. Va.). An effective use level for the surfactants is at least 0.1%, preferably at least 0.2%, and more preferably at least 0.5% by weight of the high surface energy organic material.